Chloroalkyl aryloxyalkyl sulfites as new chemicals and insecticides



Patented Nov. 14, 1950 CHLOROALKYL ARYLOXYALKYL SULFITES AS NEW CHEMICALS AND INSECTICIDES Waiter D. Harris, Naugatuck, Herman D. Tate,

Woodbridge,

and John Conn., assignors to United States Rubber Com- W. Zukel, Hamden,

pany, New York, N. Y., a corporation of New Jersey No Drawing. Application October 28, 1948, Serial No. 57,413

10 Claims.

This invention relates to improvements in insecticides, particularly for the control of mites.

The insecticides of the present invention are new compounds, namely, the di-esters of sulfurous acid wherein one of the esterifying groups is a chloroalkyl radical containing 2 to 4 carbon atoms and 1 to 3 chlorine atoms and having no chlorine atom attached to the alpha carbon atom, and the other esterifying group is a radical o1 the formula R-OX--, wherein R is selected from the class consisting of monovalent aryl hydrocarbon radicals and such radicals substituted by at least one member of the group consisting of alkyl, alkoxy, cycioalkyl, halo and ultra, and X is an alkylene radical having 2 to 4 carbon atoms. The reason for the requirement that no chlorine atom be attached to the alpha carbon atom of the chloroalkyl radical is that a chlorine attached to a carbon which is attached to an oxygen, is too reactive 9, chlorine atom. The chemicals oi the present invention may be represented by the general formula in which R is a chloroalkyl radical containing 2 to 4 carbon atoms and 1 to 3 chlorine atoms and having no chlorine atom attached to the alpha carbon atom, X is an alkylene radical having 2 to 5 (or glycol monoaryl ether). The chloroalkyl chlorosulfinate may be prepared by reacting the selected chloroalkanol containing 2 to 4 carbon atoms and 1 to 3 chlorine atoms with thionyl chloride to form the chloroalkyl chlorosulflnate. This is a well known reaction. It is desirable, but not essential, that the alpha carbon atom of the chloroalkyl radical be attached to at least one hydrogen atom since the chloro-tertiary-butyl esters are somewhat diiiicult to prepare, particularly the mono-chloro-tertiary-butyl ester. due to the tendency toward dehydration of the chlorotertiary butanols in the presence of acidic reagents. The aryloxyalkanol, or glycol mono-aryl ether, may be prepared by reacting the selected alkylene monochlorhydrin with the selected phenol. This is a well known reaction. The last two mentioned reactions. and the reaction of a chloroalkyl chlorosulfinate with an aryloxyalkanol to give a product or the present invention is illustrated by the following reactions. using the preparation of 2-chloroethy1 z-(p-methylphenoxyiethyl sulfite as an example:

0 (1) CICHICHaOH 8001, u ClCHgCHgOHCl BC] (2) HOCHiCHlC-l KOCsHcCHi HOCHIOHIOGCHICHI KCl 0 (3) CICHICHOJCI HOCILCHIOCeH CHI -0 0 ClCHzCHrOAOCHzC HsOOsHsCHI H0] The ethylene chlorhydrin in the first step may be substituted by ethylene oxide. The epichlorhydrin of the second step may also be substituted by ethylene oxide. The intermediate chlorosulflnates obtained in the first step are somewhat unstable, decomposing to sulfur dioxide and the polyhaloalkane (ethylene chloride in the above preparation). They are, however, stable enough that they can be distilled under reduced pressure and stored for a short period with only slight decomposition. The reaction oi the chloroalkyl chlorosulfinate with the aryloxyalkanol or glycol mono-aryl ether (as exemplified by the third step above) is conveniently carried out in the presence of a proton acceptor such as pyridine, dimethylaniline, or trimethylamine to sequester the hydrogen chloride, and in a solvent such as benzene, xylene or solvent naphtha. A wide variation in temperature is possible, but temperatures between 20 C. and 50" C. are most convenient. The pyridine or other hydrogen chloride sequestering agent may be omitted ii the reaction is carried out under reduced pressure or in the presence of a dry inert gas such as air or nitrogen.

Examples 01' sulfurous acid di-esters oi the present invention illustrating particularly variations in the aryloxyalkyl esterifying group are:

2-chloroethyl Z-phenoxyethyl sulfite 2-chloroethyl 2-(1-naphthoxy) -ethyl sulfite 2-chloroethyl Z-(naphthoxy) -ethyl sulfite z-chloroethyl 2-(o-chlorophenoxy) -ethyl sulfite 2-chloroethyl 2-(p-chlorophenoxy) -ethyl sulfite z-chloroethyl 2- (2,4-dichlorophenoxy ethyl sulfite 2-chloroethyl 2-(2,4,5-trichlorophenoxy) ethyl sulflte 2-chloroethyl 2-(2,4,6-trichlorophenoxy) ethyl sulfite 2-chloroethyl 2-(2,4,5,6 tetrachlorophenoxy) ethyl sulfite Z-chloroethyl 2 (pentachlorophenoxy) ethyl sulfite 2 chloroethyl 1 methyl 2 (o chloro pnitrophenoxyl-ethyl sulflte 2 chloroethyl 1 methyl 2 (p chloro onitrophenoxy) -ethyl sulflte 2 chloroethyl 1 methyl 2 (2 chloro 4- tert. butylphenoxy) -ethyl sulflte 2 chloroethyl 1 methyl 2 (2,8 dichloro- 4-tert.-butylphenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (phenoxy) ethyl sulflte 2 chloroethyl 2 methyl 2 phenoxyethyl sulflte 2 chloroethyl 2 methyl 2 (1 naphthoxy) ethyl sulflte 2 chloroethyl 2 methyl ethyl sulflte 2 chloroethyl 2 methyl 2 (o chlorophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (p chlorophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (2,4 dichiorophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (2,4,5 trichlorophenoxy)-ethyl sulflte chloroethyl 2 methyl 2 (2,4,6 trichlorophenoxyl-ethyl sulflte chloroethyl 2 methyl 2 (2,4,5,6 tetrachlorophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (pentachlorophenoxyi-ethyl sulflte chloroethyl 2 methyl 2 (p bromophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (p fluorophenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (o methylphenoxy) -ethy1 sulflte 2 chloroethyl 2 methyl 2 (m methyl- 2 (2 naphthoxy) phenoxy)-ethyl sulflte chloroethyl 2 methyl 2 (p methylphenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (p ethylphenoxy)-ethyl sulflte 2 chloroethyl 2 methyl 2 (p isopropylphenoxy) -ethyl sulflte -chloroethyl 2 methyl 2 (p isobutylphenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (o tert. butylphenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (p tert. amylphenoxy) -ethyl sulflte chloroethyl 2 methyl 2 octylphenoxyi-ethyl sulflte chloroethyl 2 -methyl 2 (o cyclohexylphenoxy) -ethyl sulflte chloroethyl 2 methyl 2 (p cyclohexylphenoxyi-ethyl sulflte 2 chloroethyl 2 methyl 2 (p methoxyphenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (4 n propyl- 2,6-dimethoxyphenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (o nitrophenoxy) -ethyl sulflte 2 chlcroethyl 2 methyl 2 (p nitrophenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (o chloro pnitrophenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (p chloro onitrophenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (2 chloro 4- tert. butylphenoxy) -ethyl sulflte 2 chloroethyl 2 methyl 2 (2,6 dichloro- 4-tert. butylphenoxy)-ethyl sulflte 2 chloroethyl 4 (p chlorophenoxy) butyl sulflte 6 2 chloroethyl 4 (p tert.

butyl sulflte Other examples 0! the suliurous acid di-esters of the present invention are those having the same aryloxyalkyl radicals as in the above list but with the 2-chloroethyl radicals of each 01 the esters substituted by another chloroalkyi radical containing 2 to 4 carbon atoms and l to 3 chlorine atoms, for example, 2,2 dichloroethyl, 2,2,2 trichloroethyl, 2 chloropropyl, 3 chloropropyl, 2,3 dichloropropyl, 2 chloroisopropyl, 1 chloromethyl 2 chloroethyl, 2,2 dichloropropyl, 3,3 dichloropropyl, 3,3,3 trichloropropyl, 2 chlorobutyl, 3 chlorobutyl, 4 chlorobutyi, 2,3 dichlorobutyl, 2,4 dichlorobutyl, 3,4 dichlorobutyl, 1,1 dimethyl 2,2,2 trichloroethyl radicals.

Specific illustrative examples oi the preparation of the compounds of the present invention are shown in Examples I to V below.

EXAMPLEI Preparation of Z-chloroethul 2- (p-chlorophenory) -ethyl sulflte butylphenon) 2-chloroethyl chlorosulflnate was prepared as follows: Thionyi chloride (70 g.) was added to ethylene chlorohydrin (40 g.) at such a rate that the temperature did not rise above 35 C. Hydrogen chloride was evolved rapidly. The mixture was allowed to stand for two days protected from the moisture oi the air by a calcium chloride tube. The reaction mixture was iractionally distilled, yielding 72 g. of 2-chloroethyl chlorosuliinate, a water-white liquid which boiled at -94 (1/30 mm.

Ethylene glycol mono-p-chlorophenyl ether was prepared as follows: Sodium (23 g.) was dissolved in 500 cc. of anhydrous alcohol in a 1 liter 3-necked flask equipped with stirrer and reflux condenser. p-Chlorophenol (128.5 g.) was added and a dropping tunnel was inserted in the third neck of the flask. The mixture was heated with stirring to reflux and ethylene chlorohydrin (80.5 g.) was added over a period of several minutes. Refluxing was continued for two hours. The sodium chloride was removed by filtration and washed with alcohol. The combined filtrates were concentrated by distillation and washed with very dilute sodium hydroxide. then with water. The solution was diluted with an equal volume of benzene, concentrated and finally fractionated under reduced pressure through a 6 inch Vigreaux column. The product (75 g.) was an almost colorless liquid which boiled at -136" C./6 mm.

The ethylene glycol mono-p-chlorophenyl ether (34.6 g.) with pyridine ('16 g.) were dissolved in 300 cc. of dry ether. The 2-chloroethyl chlorosulfinate (32.6 g.) was added at such a rate that the ether refluxed gently. The reaction mixture was stirred thoroughly throughout the addition and for one-half hour thereafter. The pyridine hydrochloride was removed by filtration. The filtrate was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled oil and the product was freetionally distilled. The main fraction 2-chloroethyl 2-(p-chlorophenoxy)-ethyl sulflte (35 g., 58% yield) was a light yellow oil which boiled at -197" C./3 mm. Refractive index, n1 1.5870.

EXAMPLEII Preparation Z-chloroethul l-methul-Z-(ptart-bowl phenom!) -eth1 l sulflte Propylene glycol mono p tert. butylphenyl ether was prepared as follows: Propylene oxide (116 g.) was added through a dropping tunnel to a solution of p-tert-butylphenol (300 g.) and sodium (4 g.) in 500 cc. of anhydrous alcohol. The resulting solution was refluxed for 18 hours. Most of the alcohol was removed by distillation and the resulting concentrate was washed with water. Fractionation through a 6 inch helix packed column under reduced pressure yielded a fore-run (31 g.) which boiled below 140 C./8 mm. The main fraction (353 g.) was a waterwhite liquid which distilled almost constantly at 140 C./ 8 mm. and solidified at about 35 to 40 C.

To a rapidly stirred solution of the propylene glycol mono-p-tert-butylphenyl ether (61.2 g.) and pyridine (29.7 g.) in 250 cc. of dry benzene, was added 2-ch1oroethyl chlorosulflnate (61.2 g.) prepared as in Example I. The reaction flask was cooled in a cold water bath throughout the addition. Stirring was continued for a few minutes after the addition was complete. The pyririne hydrochloride was removed by vacuum filtration. The filtrate was washed in cold water and dried over calcium chloride. After topping under reduced pressure, the product was distilled. The main fraction 2-chloroethyl l-methyl-2-(p-tert.- butylphenoxy) -ethyl sulfite (yield 15.5 g.) was a yellow liquid which boiled at 200-210 CJ'T mm. Refractive index, 111 1.5075.

EXAMPLE 11! Preparation of 3chlor0propyl Z-phenoxuethul sulflte 3-chloropropyl chlorosulflnate was prepared by reacting trimethylene chlorohydrin (94.5 g.) with thionyl chloride (150 cc.) according to the procedure described for the preparation of 2-chloroethyl chlorosulfinate in Example I. The mixture was allowed to stand at room temperature for 3 /2 days. A 153 g. yield of a water-white liquid which boiled at 70 C./ 3 mm. was obtained.

Ethylene glycol-monophenyl ether was prepared by reacting ethylene chlorohydrin with phenol according to the procedure described in Example I for preparing the ethylene glycol mono-p-chlorophenyl ether.

ii-chloropropyl 2-phenoxyethy1 sulflte was prepared by reacting ethyieneglycol-monophenyl ether (27.6 g.), B-chloropropyl chlorosulfinate (35.4 g.) and pyridine (16 g.) as described in Example 1. Thirty grams of a colorless liquid which boiled at 185-6 C./2 mm. was obtained. Refractive index, n1 1.5200.

EXAMPLE IV Preparation of Z-chlorocthul 3-(p-tcrL-butvl- Phenom!) 41 W! ndfltc Trlmethyi glycol mono p tert butylphenyl ether was prepared as follows: Sodium (28 g.) was dissolved in 500 cc. of anhydrous alcohol. The solution was heated to reflux as p-tert-butylphenol (150 g.) was added. Trimethylene chlorohydrin (94.5 g.) was added rapidly through a dropping funnel and refluxing was continued for 4 hours. After removing the sodium chloride by filtration the solution was concentrated by distillation. washed with dilute alkali, then with water and finally distilled under reduced pressure. The product was a water-white slightly viscous liquid which distilled at 156-162" (3J4. mm.

To a solution of the trimethylene glycol monop-tert-butylphenyl ether (41.6 g.) in benzene (250 cc.) and pyridine (19.8 g.) 2-chloroethyl chlorosulfinate (40.8 g.) prepared as in Example I, was added with stirring. The temperature was kept below 25 C. throughout by cooling in a water bath and by regulating the rate of addition. Stirring was continued for about 15 min. after addition was complete. The mixture was washed several times with water, topped and distilled under reduced pressure. The product distilled at 194- 204 C./ 1.5 mm. as a pale straw-colored liquid. Refractive index, 111 1.5132.

EXAMPLE V Preparation of 2,2,2-trichloroethyl Z-phenoxuethyl sulflte and pyridine (4 g.) in dry ether cc.) according to the procedure described in Example I. The product was a light yellow 011 (6.5 g.) which distilled at ITO-180 C./1.5 mm. Refractive index, 111 1.5364.

Boiling points and refractive indices of the above sulfite esters and various other sulflte esters prepared in the manner of the above examples are shown in the table below:

Table I Refractive Index Bulflte Ester Boiling Point (D mm) 2-chloroethyl 2phenoxyethyl Topped M165" CJZ) 111111..-. 1.537101; 22 C.

177-179" C./i.5 mm s cl 580 at 28" C 1. 2-chlnrueihyi l-n1ei yI-Q-phenoxyei l. at 2-chl0rwthyl l meihyl-lip-methylphenoxy)-eihyi 190-187 C [2 5 mm 1.51 at 24 C. 2chlnrneihyl l-mr-thyl-2-(p-nltrophenoxfl-eihgl. \ioi distilled 1.5532 at 24 C. 2-chlnrnelhyl i-methyl z (n-chlnrnphenoxylri yl. 185-187 0J2 mm 1.5m at 25 C. 2-chlorneihy] 1mothyl-2-(2Adichlorophenoxy)-ethyl. 210-22? 0.]? mm 1. 1.5369 at 28 0. Q-chivmeihyl l-mothyl-2-(ZA.5-irichiornphenoxwethyl 2222i6 C.I6 mm 1.5477 at 2B O. 2-chlomothyl l-methyl-2-(pcntachlorophenoxyl-ethyl... 285-250 0J3 mm 1.5700 at 21 C. 2-ehmm-vhyl Lmeihyl-2-(p-tort-hutylphenoxy)-eihyl. 200210 (3.]? mm 15075 at 27 C. Q-chinmcthyl l-mcihyl-2-(p-wrt-amylphenoxP-ethyl.. 1.5002 at 2i.5 C. 2-chlcmeihyl l-mcihy]-2-(6-naphthoxy)-ethy he- 228-236" 0 I4 111111.. 1.5572 at 21 C. 2-chlomeii1yl l-methyi-2-(o-isopropyiphenoxyrethyl. Mil-1W" 0 1.5150 at $1.5 C. 2-chloroethyl l-methyl-2-(m-isopro y phenoryl-ethyl. lib- 0 I1 5 mm 1.5135 at 215 0. 2-ch1oroethyl l-methyl-l-(p-znethy phenoxyl'etbylum 100-195 01/2 man- 1.581 at 0. i-oblorooihyl i-methyl-2-(o-Cl-p-tert-butyiphenoxy)othyL... mm 0.1 mm i. 200 at 115 0.

Refractive Index Bulllto Eater Boiling Point (D um) 2-chloroethyl l-methyl-24p-cyclohex lphenoxyl-ethyl 210433 J2 mm 1.5296 at 20.5 0. 2-chloroethyl 3-(p-tert-butyighenoxy -propyl 194-204 C./ 1.5132 at 21.6 0. a-chlororliropgl Z-phenoxy-et y] 1.6200 at 26" O. l-methy -2c lorocthyl z-phenoxyethyl 1.5183 at 20 0. l-methyi-Z-chloroethyl l-methyl-2-(p-ch1orophenoxy)-ethy1 1.5210 at 28 0. 2,3-dichloropropyl z-(p-tert-buty1phenoxy)-ethyl 1.5203 at 25 0. 2,3-diehloropropyl 1-methyl-Z-(p-tcrtbutylph0noXy)-cthyl. 1.5130 at 25 C. 2,2,2-tricbioroethyl Z-phenoxyethyl 1.5364 at 25 0.

The following illustrates the effectiveness of the chemicals of the invention for controlling the Greenhouse red spider mite (Teflranychus telarius).

In the test on various chemicals or the present invention against Greenhouse red spider mites, rings of an adhesive preparation non-toxic to the organisms under test, such as is used on fly papers and for ringing trees, were .placed around the borders of the upper surfaces of the leaves of growing pinto bean plants which were at the two-leaf stage. Greenhouse red spider mites were transferred to the thug treated leaves by placing infested bean leaves within the border of the adhesive preparation for 24 hours to effect transfer of the mites. The plants thus infested were then sprayed with aqueous emulsions of the various chemicals of the invention at the selected concentrations. The emulsions of the chemicals were prepared by dissolving in parts of the sulfite 1 part of a commercial surface-active dispersing agent comprising the reaction product of castor oil and ethylene oxide and known to be nontoxic at the concentrations used to organisms under test, and then adding enough water to form a 1% emulsion of the sulflte ester. In order to obtain the various concentrations of the sulfite esters, amounts of this 1% emulsion were diluted with enough water to give the proper concentration. Observations were made after 48 hours to determine the kill of the mites. The results were reported as percent mortality of the mites.

The results of the tests with the various sulflte esters of the present invention are shown in the table below:

The extreme importance of the aryloxy substituent in the alkyl group 01' the aryloxyaikyl radical is attested to by the relative inactivity against Tetranuchus telarius of the chloroalkyl unsubstituted-alkyl sulfite esters. 2-Chlorethyl ethyl sulfite gave only 5% kill of mites at 1:100 concentration, as compared with the very high mortality at much more dilute concentrations oi the 2-chloroethyl aryloxyethyl sulfltes oi the present invention, as shown in the above table.

The chemicals of the present invention may be applied in various manners for the control of insects. They may be applied to loci to be pro tected against insects in undiluted form. or as dusts when admixed with or adsorbed on powdered solid carriers. such as the various mineral silicates, e. g. mica, talc, pyrophyllite and clays, or as liquids or sprays when in a liquid carrier. as in solution in a suitable solvent, or dispersed in a suitable non-solvent medium. for example, water. In protecting plants (the term including plant parts) which are subject to attack by insects, the chemicals of the present invention are preferably applied as aqueous emulsions containing a dispersing agent. The chemicals of the invention may be admixed with powdered solid carriers. such as mineral silicates together with small amounts of a dispersing agent so that a wettable powder is obtained which may be applied directly to loci to be protected against insects. or which may be shaken up with water. to form a suspension 01' the chemical (and powdered carrier) in water for application in that form. The chemicals of the present invention may be applied to loci to be protected against insects by the aerosol method. Solutions for the aerosol Table II Per Cent Mortality of Mites at Indicated oncentrations Sulilte Ester Z-chloroethyl 2-phenoxycthyl 2-chloroethyl Z-gyrmethylphenoxfl-ethyl 2-chloroethyl 2- o chloro-phenoxytethyln 2 chlorocthyl 2-(p-chloro-phenoxy)-cthyl 2-chloroethyl 2-(2,4-dichloro-phenoxy)-cthyl 2-chloroethyl 2-(n-tert-butyl-phenoxyJ-cthyl 2-chloroethy] 2-(octyl-phcnoxy)-cthyl 2-chloroethyl l-methyLQ-phenoxy-cthyl.

2 chloroethyl l-mcthyl-2-(p-methylphenoxyl-ethyl 2-chlm'oethyl l-methyl-Z-(p-nitrophenoxy)-cthyl 2-chlorocthyl l-methyl 2-(p-chIorophenoxy)-ethyl 2-chioroethy] 1-mcthy1-2-(2,d-dichlorophcnoxw-ethyL 2-chlnroethyl l-mrthyl-2-(2,4,5-trichlorophcnoxy)-ethyl 2-chlorouthy1 l-methyl-2-(pentachlorophenoxy)-cthyl 2-chlurorthyl l-methyl-Z-(n-tert-butylphcnoxy) 2chlomethyl l-meLhy1-2-( u-tert-amylphenoxy) 2chloruethyl l-mclhy1-2-lfl-uaphthoxy)-ethyl c Z-chiorocthyl l-mcthyl-Zio-is0propylphenoxyl-cthyl 2-rhlnroethyl l-mcihyl-ii-(m-isonro ylphenoxy)-cthyl 2 chlomethyl l-mothyl-Z-(p-mr-thy phenoxyJ-cthyl 2 ch1or0rthyl lmethyl-2-(c-Cl-p-tert-hutylpi1enoxy)-ethy 2-chloroethyl l-mcihyl-2-(p-cyc1nl1cxylphenoxy)-ethyl 2-chluroelhy1 3-( p-ierl-butv1phenoxyl-propyl 3-chlnrupropyl 2-phcnoxyethyl 1-mcthyl-2-chlnmethyl 2-phonoxyothy1 l-mcthg. l-2-c11loroethyl l-methyl-2-(p-ch1orophenoxy)-ethy1 2.3-dlchloropropyl 2-(p-tert-butylphenoxy)ethyl 2,3-dichloropropyl l-methy1-2-(p-lert-buty1phenoxy)ethyl 2,2,2-trichloroethyl 2-phenoxyethyL treatment may be prepared by dissolving the chemical directly in the aerosol carrier which is liquid under pressure but which is 0. lies at ordinary temperature (e. g. 20 C.) and atmospheric pressure. or the aerosol solution may be prepared by first dissolving the chemical in a less volatile solvent and then admixing such solution with the highly volatile liquid aerosol carrier. The chemicals may be used admixed with carriers that are active of themselves, for example, other insecticides. fungicides or bactericides.

Having thus described our invention. what we claim and desire to protect by Letters Patent l. A di-ester oi suliurous acid wherein one of the esterifying groups is a chloroallryi radical containing 2 to 4 carbon atoms and l to 3 chlorine atoms and having no chlorine atom attached to the alpha carbon atom. and wherein the other esterliying group is a radical of the formula R-O-X. wherein R is selected from the class consisting of monovalent aryl hydrocarbon radicals and such radicals substituted by at least one member of the group consisting of alkyl, alkoxy. cycioaikyl. halo and nitro. and X is an alkyiene radical having 2 to 4 carbon atoms.

2. A di-ester oi suliurous acid wherein one of the esterifying groups is a radical of the formula R-OX. wherein R is selected from the class consisting of monovalent aryl hydrocarbon radicais and such radicals substituted by at least one member of the group consisting of alkyl, alkoxy, cycloalkyl, halo and nitro, and X is an alkylene radical having 2 to 4 carbon atoms, and wherein the other esteriiying group is a monochloroalkyl radical containing 2 to 4 carbon atoms in which at least one hydrogen atom is attached to the alpha carbon atom and in which the chlorine atom is attached to a carbon atom other than the alpha carbon atom.

8. Z-Chloroethyl l-methyl-Z-(p-tert-butyL phenoxy) -ethyl sulfite.

4. 2-Chloroethy1 2-(p-chlorophenoxy) -ethyl sulfite.

5. 2-Ch1oroethyl 3- (p-tert-butylphenoxy) pro pyl sulflte.

6. A composition comprising a di-ester of sulfurous acid wherein one of the esterifying groups is a chloroalkyl radical containing 2 to 4 carbon atoms and 1 to 3 chlorine atoms and having no chlorine atom attached to the alpha carbon atom, and wherein the other esterii'ying group is a radical of the formula RO-X. wherein R is selected from the class consistin of monovalent aryl hydrocarbon radicals and such radicals substituted by at least one member of the group consisting of alkyi, alkoxy, cycloalkyl, halo and nitro. and X is an alkylene radical having 2 to 4 carbon atoms. and a surface-active dispersing agent.

7. A composition comprising a di-ester oi sulturous acid wherein one of the esterifying groups is a radical of the formula R--O-X, wherein R is selected from the class consisting of monovalent aryl hydrocarbon radicals and such radicals substituted by at least one member of the group consisting of alkyl, alkoxy. cycloalkyl. halo and nitro. and x is an alkylene radical havin 2 to 4 carbon atoms, and wherein the other esteriiying group is a monochloroalkyi radical containing 2 to 4 carbon atoms in which at least one hydrogen atom is attached to the alpha carbon atom and in which the chlorine atom is attached to a carbon atom other than the alpha carbon atom, and a surface-active dispersing agent.

8. A composition comprising 2-chloroethyl 1- methyl 2 (p tert. butylphenoxy) ethyl sulflte, and a surface-active dispersing agent.

9. A composition comprising 2-chloroethyi 2- (pchlorophenoxy)-ethyl sulflte, and a surfaceactive dispersing agent.

10. A composition comprising 2-chloroethyl 3- (p-tert-butylphenoxy)-pr0pyl sultlte, and a surface-active dispersing agent.

WALTER Di HARRIS. HERMAN D. TATE. JOHN W. ZUKEL.

REFERENCES CITED UNITED STATES PATENTS Name Date Hechenbleikner May 26, 1945 OTHER REFERENCES Carre et al: Bull. soc. chim. France;" 4th series Vol. 53 (pt. 2) 1933 pp. 1070-75.

Number 

7. A COMPOSITION COMPRISING A DI-ESTER OF SULFUROUS ACID WHEREIN ONE OF THE ESTERIFYING GROUPS IS A RADICAL OF THE FORMULA R-O-X-, WHEREIN R, IS SELECTED FROM THE CLASS CONSISTING OF MONOVALENT ARYL HYDROCARBON RADICALS AND SUCH RADICALS SUBSTITUTED BY AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF ALKYL, ALKOXY, CYCLOALKYL, HALO AND NITRO, AND X IS AN ALKYLENE RADICAL HAVING 2 TO 4 CARBON ATOMS; AND WHEREIN THE OTHER ESTERIFYING GROUP IS A MONOCHLOROALKYL RADICAL CONTAINING 2 TO 4 CARBON ATOMS IN WHICH AT LEAST ONE HYDROGEN ATOM IS ATTACHED TO THE ALPHA CARBON ATOM AND IN WHICH THE CHLORINE ATOM IS ATTACHED TO A CARBON ATOM OTHER THAN THE ALPHA CARBON ATOM, AND A SURFACE-ACTIVE DISPERSING AGENT. 